Insecticidal and miticidal compositions

ABSTRACT

The invention relates to an insecticidal and miticidal composition which contains as active ingredients chlorfenapyr in combination with one or more organophosphoric acid ester-type compounds and to a method for controlling insecticidal or miticidal pests which have acquired resistance to commercial insecticidal and miticidal agents.

This application is a 371 of PCT/JP97/04497, filed Dec. 8, 1997.

FIELD OF THE INVENTION

This invention relates to insecticidal and miticidal compositions whichcan be effectively applied in the agrohorticultural field. In moredetail, it relates to insecticidal and miticidal compositions whichcontain two or more active ingredients and are especially effectiveagainst pests and mites which have acquired resistance to commercialinsecticidal and miticidal agents.

BACKGROUND OF THE INVENTION

4-Bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (hereinafter referred to aschlorfenapyr), which is an active ingredient of the insecticidal andmiticidal composition of the invention, is known to be effective againstinsects such as Hemiptera pests such as leafhoppers (Dolto cephalidae),Lepidoptera pests such as diamond back moth (Plutella xylostella),common cutworm (Spodoptera litura) and apple leafminer (Phyllonorycterringoniella) and Thysanoptera pests such as Thrips palmi and yellow teathrips (Spirtothrips dorsalis) and agrohorticultural pests such as mitessuch as two-spotted spider mite (Tetranychus urticae koch), Kanzawaspider mite (Tetranychus kanzawai kishida) and Aculops pelekassi[Japanese Laid-open (Kokai) Patent Publication No. 104042/89].

The second active ingredient of the insecticidal and miticidalcomposition of the invention includes one or more of theorganophosphoric acid ester-type compounds which are known to beeffective insecticidal and miticidal agents against agrohorticulturalpests such as Hemiptera, Lepidoptera and Coleoptera insects and mites,and fungicidal agents against blast and soil born diseases of paddyrice.

Although insecticidal and miticidal agents have been developed in orderto control various pests such as agrohorticultural pests or hygienicpests and in practice have been used as a single or a mixed agent, pestswhich have acquired resistance against various agents have beenappearing as a result or the repeated use of these agents.

In particular, important economic pests in agrohorticulture such asspider mites (Tetranychidae), which have a propensity to easily developresistance against pesticidal agents due to their ability to depositlarge numbers of eggs and produce large numbers of generations which,themselves, require only a few days for development are of greatconcern. Resistance development in this pest family is also favored by ahigh mutation rate and frequent inbreeding, due to minimal migration.For these reasons, two-spotted spider mite (Tetranychus urticae koch),Kanzawa spider mite (Tetranychus kanzawai kishida), Aculops pelekassi,and the like have acquired resistance, to some degree, against almostall existing pesticidal agents. Therefore, in order to prevent andcontrol the damage caused by spider mites, development of a newinsecticidal and miticidal agent which shows a high effect againstspider mites which have acquired resistance against the conventionalmiticidal agents is highly desirable.

However, to obtain an insecticidal and miticidal composition which showsno cross-resistance with existing insecticidal and miticidal agents, hasno toxicity problems and has little negative impact on the environment,is extremely difficult. Therefore, a means to delay or prevent thedevelopment of resistant strains of pest species is always being sought.In order to apply an effective agent as long as possible, a rotationalapplication of agents with different mechanisms of action is adopted forgood pest management practice.

However, this approach does not necessarily give satisfactory pestcontrol. Therefore, after a resistance problem has occurred, acountermeasure to resistance by combining insecticidal and miticidalagents has been studied. However, a high synergistic action has notalways been found.

Therefore, it is an object of this invention to provide an insecticidaland miticidal composition which demonstrates a high controlling effecteven against spider mites which have acquired resistance againstchlorfenapyr.

SUMMARY OF THE INVENTION

In order to establish a countermeasure to a resistance problem in spidermites against chlorfenapyr before such a problem occurs, the synergisticaction with the existing insecticidal, miticidal and fungicidal agentswas studied using resistant species which have been artificiallyestablished in the laboratory by selecting spider mites which have beentreated with chlorfenapyr. Thus, it has now been found that aninsecticidal and miticidal composition which contains as activeingredient chlorfenapyr in combination with at least one of thedesignated organophosphoric acid ester-type compounds shows a jointaction or synergistic effect which could not be foreseen from eachindividual ingredient alone.

DETAILED DESCRIPTION OF THE INVENTION

The insecticidal and miticidal composition of the invention isparticularly effective for the control of spider mites such astwo-spotted spider mites (Tetranychus urticae koch). Tetranychuscinnabarinus (Boisduval), Kanzawa spider mite (Tetranychus kanzawaikishida), hawthorn spider mite (Tetranychus viennensis zacher), and thelike.

Advantageously, the insecticidal and miticidal composition of theinvention shows not only a synergistic miticidal effect against theabove-mentioned spider mites, but also demonstrates simultaneous controlof troublesome pests such as leafroller moths (Tortricidae),Carposinidae, leafminer moths (Lyonetiidae), plant bugs (Pentatomidae),aphids (Aphididae), leafhoppers (Deltociphalidae), Coccinea, thrips(Thripidae), diamond back moths (Plutella xylostella), Mamestrabrassicae, leaf beetles (Chrysomelidae), whiteflies (Aleyrodidae) andthe like on important agronomic crops such as fruit trees, for examplecitrus, apple and pear; tea plants; vegetables and the like.

Chlorfenapyr, which is an active ingredient of the insecticidal andmiticidal composition of the invention, is a known compound described inJapanese Laid-open (Kokai) Patent Publication No. 104042/89 and its wayof using as agrohorticultural insecticidal and miticidal agent is shownin the Publication. It can also be easily synthesized according to themethod described in the Publication.

Organophosphoric acid ester-type compounds which are suitable for use asthe second active ingredient in the composition of the invention arecompounds represented by the general formulae (I) or (II),

wherein

X represents oxygen atom or sulfur atom,

Y represents oxygen atom or sulfur atom, group represented by—S(CH₂)_(n)S— (n is 1 or 2) or single bond,

R¹ represents C₁-C₆ alkyl group,

R² represents C₁-C₈ alkoxy group, C₁-C₈ alkylthio group, C₁-C₄alkylcarbonylamino group, C₁-C₆ alkylamino group or phenyl group, and

R³ represents C₁-C₈ alkyl group, C₂-C₆ alkenyl group, amino group,phenyl group, or heteroaryl group, which are unsubstituted orsubstituted by 1 to 4 same or different substituents selected from thesubstituent group A mentioned below, or the following formula (III)

(wherein R¹, R² and X mean the same as the above-mentioned).

Substituent group A: C₁-C₈ alkyl group, C₁-C₈ alkoxy group, C₁-C₆aliphatic acyl group, C₁-C₆ alkoxycarbonyl group, C₁-C₆ alkylthio group,C₁-C₆ alkylamino group, di-C₁-C₆ alkylamino group, C₁-C₄ alkylsulfinylgroup, C₁-C₄ haloalkyl group, N—C₁-C₄ alkylcarbamoyl group, N,N-di-C₁-C₄alkylcarbamoyl group, N—C₁-C₄ alkyl-N-formylcarbamoyl group, heteroarylgroup which may be substituted, phenyl group which may be substituted,halogen atom, nitro group, cyano group, hydroxy group and acetylaminogroup.

In the general formulae (I) and (III), the “C₁-C₆ alkyl group” in thedefinition of R¹ is a straight chain or branched chain alkyl group with1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl,2-methylbutyl, neopentyl, 1-ethyl-propyl, n-hexyl, 4-methylpentyl,3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl,2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethylbutyl.

In the general formulae (I) and (III), “C₁-C₈ alkoxy group” in thedefinition of R² is a straight chain or branched chain alkoxy group with1 to 8 carbon atoms, such as, for example, methoxy, ethoxy, n-propoxy,i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, i-pentoxy,2-methylbutoxy, neopentoxy, n-hexyloxy, 4-methylpentoxy,3-methylpentoxy, 2-methyl-pentoxy, 3,3-dimethylbutoxy,2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy,1,3-dimethylbutoxy, 2,3-dimethylbutoxy, n-hepty(oxy and n-octyloxy.

The “C₁-C₈ alkylthio group” in the definition of R² is a straight chainor branched chain alkylthio group with 1 to 8 carbon atoms, such as, forexample, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,n-pentylthio, n-hexylthio, n-heptylthio and n-octylthio.

The “C₁-C₄ alkylcarbonylamino group” in the definition of R² is acarbonylamino group, to which a straight chain or branched chain alkylgroup with 1 to 4 carbon atoms is bound, such as, for example,methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino,i-propylcarbonylamino, n-butylcarbonylamino. s-butylcarbonylamino andt-butylcarbonylamino.

The “C₁-C₆ alkylamino group” in the definition of R² is an amino group,to which a straight chain or branched chain alkyl group with 1 to 6carbon atoms is bound, such as, for example, methylamino, ethylamino,n-propylamino, i-propylamino, n-butylamino, i-butylamino, s-butylamino,t-butylamino, n-pentylamino and n-hexylamino.

In the general formulae (I) and (II), the “C₁-C₈ alkyl group” in thedefinition of R³ and the substituent group A is a straight chain orbranched chain alkyl group with 1 to 8 carbon atoms, such as, forexample, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,t-butyl, n-pentyl, i-pentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl,n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl,3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl,n-heptyl and n-octyl.

The “C₂-C₆ alkenyl group” in the definition of R³ is a straight chain orbranched chain alkenyl group with 2 to 6 carbon atoms, such as, forexample, vinyl, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl,2-methyl-1-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 1-butenyl,2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl1-2-butenyl,1-ethyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,1-ethyl-3-butenyl, 1-pentenyl, 2-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl,2-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and5-hexenyl.

The “heteroaryl group” in the definition of R³ and the substituent groupA is a 5- to 8-membered heterocyclic group, which may be condensed andcontains 1 to 5 same or different atoms selected from oxygen atom,sulfur atom and nitrogen atom, such as, for example, furanyl, thienyl,pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, thianyl, pyridyl,pyridazinyl, pyrazolyl, imidazolyl, triazinyl, thiadiazolyl,imidazothiazolyl, benzoisoxazolyl, chromenyl, quinolinyl, benzothianyl,quinixalinyl and benzotriazinyl.

The “C₁-C₈ alkoxy group” in the definition of the substituent group A isa straight chain or branched chain alkoxy group with 1 to 8 carbonatoms, such as, for example, methoxy, ethoxy, n-propoxy, i-propoxy,n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, i-pentoxy,2-methylbutoxy, neopentoxy, n-hexyloxy, 4-methylpentoxy,3-methylpentoxy, 2-methylpentoxy, 3,3-dimethylbutoxy,2,2-dimethylbutoxy, 1,1-dimethyl-butoxy, 1,2-dimethylbutoxy,1,3-dimethylbutoxy, 2,3-dimethylbutoxy, n-heptyloxy and n-octyloxy.

The “C₁-C₆ aliphatic acyl group” in the definition of the substituentgroup A is a straight chain or branched chain aliphatic acyl group withtotal carbon atoms of 1 to 6, such as, for example, formyl, acetyl,propionyl, butyryl and valeryl.

The “C₁-C₆ alkoxycarbonyl group” in the definition of the substituentgroup A is a carbonyl group, to which a straight chain or branched chainalkoxy group with 1 to 6 carbon atoms is bound, such as, for example,methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl,i-butoxycarbonyl, t-butoxycarbonyl, n-pentoxycarbonyl andn-hexyloxycarbonyl.

The “C₁-C₆ alkylthio group” in the definition of the substituent group Ais a straight chain or branched chain alkylthio group with 1 to 6 carbonatoms, such as, for example, methylthio, ethylthio, n-propylthio,i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,n-pentylthio and n-hexylthio.

The “C₁-C₆ alkylamino group” in the definition of the substituent groupA is an amino group, to which a straight chain or branched chain alkylgroup with 1 to 6 carbon atoms is bound, such as, for example,methylamino, ethylamino, n-propylamino, i-propylamino, n-butylamino,i-butylamino, s-butylamino, t-butylamino, n-pentylamino andn-hexylamino.

The “Di-C₁-C₆ alkylamino group” in the definition of the substituentgroup A is an amino group, to which two same or different straight chainor branched chain alkyl groups with 1 to 6 carbon atoms are bound, suchas, for example, dimethylamino, diethylamino, methylethylamino,dipropylamino and dibutylamino.

The “C₁-C₄ alkylsulfinyl group” in the definition of the substituentgroup A is a sulfinyl group, to which a straight chain or branched chainalkyl group with 1 to 4 carbon atoms is bound, such as, for example,methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl,n-butylsulfinyl, i-butylsulfinyl, s-butylsulfinyl and t-butylsulfinyl.

The “C₁ -C₄ haloalkyl group” in the definition of the substituent groupA is a straight chain or branched chain haloalkyl group with 1 to 4carbon atoms, such as, for example, fluoromethyl, chloromethyl,bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl,trifluoromethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl,2-bromoethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl,3-bromopropyl, 2,2,3,3,3-pentafluoropropyl,2,2,2-trifluoro-1-methylethyl, 4-fluorobutyl, 4-chlorobutyl,4-bromobutyl and 2,2,3,3,4,4,4-heptafluorobutyl.

The “N—C₁-C₄ alkylcarbamoyl group” in the definition of the substituentgroup A is a carbamoyl group, to which a straight chain or branchedchain alkyl group with 1 to 4 carbon atoms is bound, such as, forexample, N-methylcarbamoyl, N-ethyl-carbamoyl, N-n-propylcarbamoyl,N-i-propylcarbamoyl, N-n-butylcarbamoyl, N-i-butylcarbamoyl,N-s-butylcarbamoyl and N-t-butylcarbamoyl.

The “N,N-di-C₁-C₄ alkylcarbamoyl group” in the definition of thesubstituent group A is a carbamoyl group, to which two same or differentstraight chain or branched chain alkyl groups with 1 to 6 carbon atomsare bound, such as, for example, N,N-dimethylcarbamoyl,N,N-diethylcarbamoyl, N-ethyl-N-methylcarbamoyl,N-methyl-N-propylcarbamoyl and N-i-propyl-N-methylcarbamoyl.

The “N—C₁-C₄ alkyl-N-formylcarbamoyl group” in the definition of thesubstituent group A is a formylcarbamoyl group, to which a straightchain or branched chain alkyl group with 1 to 4 carbon atoms is bound,such as, for example, N-formyl-N-methylcarbamoyl,N-ethyl-N-formylcarbamoyl, N-formyl-N-n-propylcarbamoyl,N-formyl-N-i-propylcarbamoyl. N-formyl-N-n-butylcarbamoyl,N-formyl-N-i-butylcarbamoyl, N-formyl-N-s-butylcarbamoyl andN-formyl-N-t-butylcarbamoyl.

The “halogen atom” in the definition of the substituent group A is, forexample, fluorine atom, chlorine atom, bromine atom and iodine atom.

Among the generic names and chemical names exemplary of theorganophosphoric acid esters represented by the general formulae (I) and(II) are those names shown below. These examples, however, are notintended to limit the scope of the invention.

Generic name: Chemical name

BRP: Dimethyl-1,2-dibromo-2,2-dichloroethylphosphate

CVMP: 2-Chloro-1-(2,4,5-trichlorophenyl)vinyidimethylphosphate

CVP: 2-Chloro-1-(2,4-dichlorophenyl)vinyldiethylphosphate

CYAP: O,O-Dimethyl-O-p-cyanophenylthiophosphate

DDVP: Dimethyl-2,2-dichlorovinylphosphate

DEP: Dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate

DMTP:O,O-Dimethyl-S[5-methoxy-1,3,4-thiadiazol-2(3H)nyl-(3)-methyl]dithiophosphate

EPN: Ethyl p-nitrophenylthionobenzenephosphonate

ESP: Dimethylethylsulfinylisopropylthiophosphate

IBP: O,O-Diisopropyl-S-benzylthiophosphate

MEP: O,O-Dimethyl-O-(3-methyl-4-nitrophenyl)thiophosphate

MPP: O,O-Dimethyl-O-[3-methyl-4-(methylthio)phenyl]thiophosphate

PAP: Ethyl dimethyldithiophosphorylphenylacetate

PMP: O,O-Dimethyl-S-phthalimidomethyldithiophosphate

Acephate: O,S-Dimethyl-N-acetylphosphoroamidothioate

Isoxathion: O,O-Diethyl-O-(5-phenyl-3-isoxazolyl)phosphorothioate

Isofenphos:O-Ethyl-O-2-isopropoxycarbonylphenylisopropylphosphoramidothioate

Ethion: O,O,O′,O′-Tetraethyl-S,S′-methylenebisphosphorodithioate

Ethylthiometon: O,O-Diethyl-S-2-(ethylthio)ethylphosphorodithioate

Etrimfos: O-6-Ethoxy-2-ethylpyrimidin-4-yl-O,O-dimethylphosphorothioate

Quinalphos: O,O-Diethyl-O-quinoxalin-2-yl-phosphorothioate

Chlorpyrifos: O,O-Diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate

Chlorpyrifosmethyl:O,O-Dimethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate

Salithion: 2-Methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide

Dimethylvinphos: 2-Chloro-1-(2,4-dichlorophenyl)vinyldimethylphosphate

Dimethoate: O,O-Dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate

Sulprofos: O-Ethyl-O-4-methylthiophenyl-S-propyl-phosphorodithioate

Diazinon: (2-Isopropyl-4-methylpyrimidyl-6)-diethylthiophosphate

Thiometon: Dimethyl-S-ethylthioethyldithiophosphate

Vomidothion: Dimethyl-methylcarbamoylethylthioethylphosphorothioate

Pyraclofos:(RS)-(O-1-(4-chlorophenyl)-pyrazol-4-yl)-O-ethyl-S-propyl-phosphorothioate

Pyridaphenthion:O,O-Diethyl-O-(3-oxo-2-phenyl-2H-pyridazin-6-yl)phosphorothioate

Pirimiphosmethyl:2-Diethylamino-6-methylpyrimidin-4-yl-dimethylphosphorothioate

Prothiophos: O-2,4-Dichlorophenyl-O-ethyl-S-propylphosphorodithioate

Propaphos: O,O-Dipropyl-O-4-methylthiophenylphosphate

Profenofos: O-4-bromo-2-chlorophenyl-O-ethyl-S-propyl-phosphorothioate

Phosalone: 3-Diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone

Formothion: O,O-Dimethyl-S-(N-methyl-N-formoylcarbamoyl)dithiophosphate

Malathon: Dimethyldicarbethoxyethyldithiophosphate

Monocrotophos: 3-(Dimethoxyphosphinyloxy)-N-methyl-cis-crotonamide

The above-mentioned names of insecticidal and fungicidal agents aregeneric names described in “Agrochemicals Handbook 1992 Edition”published on Jul. 30, 1992 by Japan Plant Protection Association and“SHIBUYA INDEX-1996-(7th Edition)” published on Apr. 1, 1996 by ZENNOH.

In this invention, among the above-mentioned agents, especiallyO,O-dimethyl-O-p-cyanophenylthiophosphate (CYAP),ethylparanitrophenylthionobenzenephosphonate (EPN),O,O-disopropyl-S-benzylthiophosphate (IBP),O,O-dimethyl-O-(3-methyl-4-nitrophenyl)thiophosphate (MEP),O,O-dimethyl-O-[3-methyl-4-(methylthio)phenyl]-thiophosphate (MPP),ethyl dimethyldithiophosphorylphenylacetate (PAP),O,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate (Ethion),O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate (Chlorpyrifos),O,O-dimethyl-O-3,5.6-trichloro-2-pyridylphosphorothioate(Chlorpyrifosmethyl),O-ethyl-O-4-methylthiophenyl-S-propyl-phosphorodithioate (Sulprofos),(2-isopropyl-4-methylpyrimidyl-6)-diethylthiophosphate (Diazinon),O,O-diethyl-O-(3-oxo-2-phenyl-2H-pyridazin-6-yl)phosphorothioate(Pyridaphenthion),O-2,4-dichlorophenyl-O-ethyl-S-propylphosphorodithioate (Prothiophos),3-diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone (Phosalone) anddimethyidicarbethoxyethyidithiophosphate (Malathon) are preferable dueto a high synergistic action with chlorfenapyr.

For the preparation of the insecticidal and miticidal composition of theinvention, it is suitable to formulate as a wettable powder, aqueousconcentrate, emulsion, liquid concentrate, sol (flowable agent), powder,aerosol, or the like, by conventional methods such as admixingchlorfenapyr and organophosphoric acid ester-type compound(s) with asuitable carrier and auxilliaries, such as emulsifiers, dispersants,stabilizers, suspending agents, penetrants, and the like.

The content of the total active ingredients of the composition of theinvention, expressed as weight/weight %, is preferably in the range ofabout 1-90% for wettable powder, aqueous concentrate, emulsion, liquidconcentrate and sol formulations. The preferable content of total activeingredients is about 0.5-10% for powder formulations and about 0.01-2%for aerosol formulations.

Carriers suitable for use in the insecticidal and miticidal compositionsof the invention may be any solid or liquid carrier which is commonlyused for an agrohorticultural composition. Various surfactants,stabilizers and other auxiliary ingredients may be used according to thenecessity.

In commercially useful formulations, the composition of the inventionmay also be present in a mixture with other active agents, for examplevarious insecticidal, miticidal, fungicidal and herbicidal agents, plantgrowth regulators, repellants, attractants, synergists and fertilizersand fragrances, in order to expand its applicability.

The ratio of chlorfenapyr to the organophosphoric acid ester-typecompound(s) in the insecticidal and miticidal composition of theinvention is about 1 weight part of chlorfenapyr to about 0.01-100weight parts, preferably about 0.5-20 weight parts, of anorganophosphoric acid ester-type compound(s).

Although the application amount may differ according to prevailingconditions such as the population density, the kinds and cultivationform of the target crop, the weather conditions, the manner ofapplication, and the like, in general, the total amount of chlorfenapyrin combination with the organophosphoric acid ester-type compound(s) isabout 0.1-1,000 g, preferably about 20-500 g, per 10 ares. In actualpractice, the composition of the invention when in the form of awettable powder, aqueous concentrate, emulsion, liquid concentrate, sol,or the like may be diluted with water and applied to the crop at anapplication rate of about 100-700 liters per 10 ares. When the inventivecomposition is formulated as a powder or aerosol, the crop may betreated with the undiluted formulation.

The insecticidal and miticidal composition of the invention is furtherillustrated in the examples set forth hereinbelow. These examples arenot intended to limit the scope of the invention. The parts all meanweight parts.

EXAMPLE 1

FORMULATION EXAMPLE 1 EMULSION Clorfenapyr  5 parts CYAP 40 parts Xylene25 parts Dimethyl formamide 20 parts Sorpol 3005X 10 parts(Polyoxyethylene type surfactant manufactured by Toho Chemical IndustryLtd. commercial name)

An emulsion is obtained by mixing homogeneously and dissolving theabove-mentioned ingredients.

EXAMPLE 2

FORMULATION EXAMPLE 2 WETTABLE POWDER Chlorfenapyr  5 parts PAP 50 partsCarplex #80 15 parts (White carbon manufactured by Shionogi & Co. Ltd.,commercial name) Zeeklite SP 22 parts (Mixture of kaolinite and cericitemanufactured by Zeeklite Ind., commercial name) Calcium ligninsulfonate 8 parts

A wettable powder is obtained by homogeneously mixing theabove-mentioned ingredients by jet air mill.

EXAMPLE 3

FORMULATION EXAMPLE 3 SOL (FLOWABLE AGENT) Chlorfenapyr   5 partsChlorpyrifosmethyl   25 parts Ethylene glycol   8 parts Sorpol AC3020  5 parts (Toho Chemical Ind. Co., Ltd., commercial name) Xanthan gum 0.1 parts Water 56.9 parts

Chlorfenapyr, chlorpyrifosmethyl and a previously prepared mixture ofethylene glycol, Sorpol AC3020 and xanthan gum are well mixed in waterand dispersed. This slurry is then wet pulverized by Dynomill (ShinmaruEnterprises) to obtain a sol (flowable agent).

EXAMPLE 4

FORMULATION EXAMPLE 4 POWDER Chlorfenapyr 0.5 parts MEP 3.5 parts Whitecarbon   5 parts Clay  91 parts (Nippon Talc Co. Ltd., commercial name)

The above-mentioned ingredients are homogeneously mixed and pulverizedto obtain a powder.

Each of the above-prepared formulations is suitable to be used as anagrochemical.

EXAMPLE 5 Test Example 1

In this experiment, the miticidal effect against female imagines(adults) of Kanzawa spider mite (Tetranychus kanzawai kishida) which areresistant to chlorfenapyr is evaluated.

Round leaf disks (2 cm diameter) are cut out of a first leaf of kidneybean by a leaf punch and 4 sheets of the disks are placed on wetsanitary cotton in a plastic cup (8 cm diameter). On each leaf disk, 4female imagines of Kanzawa spider mite (Tetranychus kanzawai kishida)which had acquired a strong resistance to chlorfenapyr are inoculated.

After the inoculation, chlorfenapyr and an organophosphoric acidester-type compound(s) are dispersed in water containing 200 ppm of anextender (Sorpol 3005X manufactured by Toho Chemical Industry Ltd.) anddiluted such that a predetermined concentration of active ingredient isobtained. Each plastic cup is sprayed with 3.5 ml of a test solutionwith a rotary spray tower (Mizuho Scientific Co., Ltd.) and stored in aconstant temperature chamber held at 25±1° C. (32 individuals are testedper concentration, 4-5 concentrations are evaluated per formulation and2 performances are repeated). Two days after treatment, the number ofliving and dead female imagines of Kanzawa spider mite (Tetranychuskanzawai kishida) which had acquired a strong resistance to chlorfenapyris counted and the mortality (%) is calculated according to the formulashown hereinbelow.$\text{Mortality (\%)} = {\frac{\text{Number of dead mite}}{\text{Number of living mite} + \text{Number of dead mite}} \times 100}$

Using these data, the LC₅₀ values are obtained by conventional probitanalysis techniques. A co-toxicity coefficient is calculated by applyingSun and Johnson's formula (J. Econ. Ent., Vol 53, p. 887, 1960) which isgenerally used to determine the degree of synergistic activity.

The LC₅₀ value of each individual effective ingredient which constitutesthe insecticidal and miticidal composition of the invention is shown inTable I. The LC₅₀ values and the co-toxicity coefficients of thecomposition of the invention are shown in Table II.

Co-toxicity coefficient=T^(c)$T^{c} = {\frac{\text{Actual toxicity index of mixture}}{\text{Theoretical toxicity index of mixture}} \times 100}$

For T^(c) values greater than 100, the greater value indicates astronger synergistic action. For a T^(c) value equal to 100, an additiveaction is indicated. For T^(c) values less than 100, the lesser valueindicates a greater antagonistic action. A more detailed description ofthe calculation or the co-toxicity coefficient using theabove-referenced Sun and Johnson formula follows.

The LC₅₀ values of Test Compound A alone and Test Compound B alone andthe LC₅₀ value of the (A+B) mixture M are determined.

Actual toxicity index of mixture M=M^(ti)

Each LC₅₀ value of effective ingredient A and effective ingredient B andthe LC₅₀ value of the mixture of A+B are used to determine the actualtoxicity index as shown in the equation below.$M^{ti} = {\frac{{LC}_{50}\quad {of}\quad A}{{LC}_{50}\quad {of}\quad M} \times 100}$

Theoretical toxicity index of mixture M=Th.M^(ti)

Th.M^(ti)=Toxicity index of A×%A in M+Toxicity index of B×%B in M

Toxicity index of B=B^(ti)$B^{ti} = {\frac{{LC}_{50}\quad {of}\quad A}{{LC}_{50}\quad {of}\quad B} \times 100}$

Toxicity index of A=A^(ti)

A ^(ti)=100

TABLE I Evaluation Of The Effect Of Test Compounds Against Female ImagoOf Kanzawa Spider Mite Which Have Acquired Resistance AgainstChlorfenapyr TEST COMPOUND LC₅₀ (ppm) Chlorfenapyr 1500 CYAP 3200 EPN3100 IBP 1300 MEP 3200 MPP 1100 PAP 2000 Ethion 3100 Chlorpyrifos 3200Chlorpyrifosmethyl  790 Sulprofos  320 Diazinon 3200 Pyridaphenthion1900 Prothiophos  260 Phosalone  350 Malathon 3400

The tested mite was a female imago of the chlorfenapyr-resistant strainof Kanzawa spider mite which was obtained by a long artificial selectionprocedure against chlorfenapyr in a laboratory on a colony of Kanzawaspider mite which had been collected in the field. As the LC₅₀ value forchlorfenapyr against a susceptible strain of spider mite is about 5 ppm,this strain has developed about a 300-fold resistance to chlorfonapyr.

As this Kanzawa spider mite was from a colony which had acquiredresistance to organophosphoric acid esters already at the time ofcollection in the field, all the tested organophosphoric acid estersshowed only low miticidal effects.

TABLE II Evaluation Of The Effect Of Test Mixtures Against Female ImagoOf Kanzawa Spider Mite Which Have Acquired Resistance AgainstChlorfenapyr RATIO (Chlorfenapyr:other LC₅₀ TEST MIXTURE ingredient)(ppm) T^(C) Chlorfenapyr + CYAP 1:8  310 920 Chlorfenapyr + EPN 1:9  300930 Chlorfenapyr + IBP 1:12 460 290 Chlorfenapyr + MEP 1:11 130 2300Chlorfenapyr + MPP 1:10 290 390 Chlorfenapyr + PAP 1:10 180 1100Chlorfenapyr + Ethion 1:10 120 2400 Chlorfenapyr + Chlorpyrifos 1:8  2201300 Chlorfenapyr + Chlorpyrifosmethyl 1:5  97 880 Chlorfenapyr +Sulprofos 3:20 170 210 Chlorfenapyr + Diazinon 5:34 430 650Chlorfenapyr + Pyridaphenthion 1:10 340 550 Chlorfenapyr + Prothiophos1:9  100 280 Chlorfenapyr + Phosalone 1:7  180 220 Chlorfenapyr +Malathon 1:10 370 820

As can be seen from the data on Table II, the co-toxicity coefficient ofthe test mixtures is a value greater than 100, which is indicative ofstrong synergistic action between chlorphenapyr and the organophosphoricacid ester-type compound(s). Though the detailed mechanism of thesynergistic action of the composition of the invention is not clear, itis estimated that the metabolic system (group of enzymes), with whichthe spider mites, which has developed resistance to chlorfenapyr,detoxifies and decomposes the compound, be inhibited by anorganophosphoric acid ester-type compound(s) to demonstrate such anaction. Therefore, a second ingredient of the insecticidal and miticidalcomposition is thought not to be limited to the organophosphoric acidester-type compounds tested in the above-mentioned examples and theorganophosphoric acid ester-type compounds specifically named above.

What is claimed is:
 1. An insecticidal or miticidal composition whichcontains as active ingredients synergistic amounts of chlorfenapyr andone or more compounds of formula I

wherein X is oxygen or sulfur; Y is —S(CH₂)_(n)S—, wherein n is 1 or 2;R¹ is C₁-C₆ alkyl; R² is C₁-C₈ alkoxy, C₁-C₈ alkylthio, C₁-C₄alkylcarbonylamino, C₁-C₆ alkylamino or phenyl, and R³ is

wherein R¹, R², and X are as defined above.
 2. The composition of claim1 wherein chlorfenapyr is present in a ratio of about 1 weight part toabout 0.01-100 total weight parts of the compound of formula I.
 3. Thecomposition of claim 1 wherein the compound of formula I isO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 4. Thecomposition of claim 3 wherein chlorfenapyr is present in a ratio ofabout 1 weight part to about 0.01-100 total weight parts ofO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 5. Thecomposition of claim 4 wherein chlorfenapyr is present in a ratio ofabout 1 weight part of chlorfenapyr to about 0.5-20 weight parts ofO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 6. A processfor the preparation of a composition of claim 1 which comprises admixingthe active ingredients with an agrohorticulturally acceptable solid orliquid carrier.
 7. The process of claim 6 wherein the active ingredientscomprise chlorphenapyr andO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 8. The processof claim 7 wherein chlorfenapyr is present in a ratio of about 1 weightpart of chlorfenapyr to about 0.5-20 weight parts ofO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 9. A method ofcontrolling insecticidal or miticidal pests which have acquiredresistance to chlorphenapyr at a locus which comprises applying to thelocus an effective amount of an insecticidal and miticidal compositioncomprising as active ingredients synergistic amounts of chlorphenapyrand one or more compounds of formula I

wherein X is oxygen or sulfur; Y is —S(CH₂)_(n)S—, wherein n is 1 or 2;R¹ is C₁-C₆ alkyl; R² is C₁-C₈ alkoxy, C₁-C₈ alkylthio, C₁-C₄alkylcarbonylamino, C₁-C₆ alkylamino or phenyl, and R³ is

wherein R¹, R², and X are as defined above.
 10. The method of claim 9wherein chlorfenapyr is present in a ratio of about 1 weight part toabout 0.01-100 total weight parts of the compound of formula I.
 11. Thecomposition of claim 9 wherein the compound of formula I isO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 12. Thecomposition of claim 11 wherein chlorfenapyr is present in a ratio ofabout 1 weight part to about 0.01-100 total weight parts ofO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.
 13. Thecomposition of claim 12 wherein chlorfenapyr is present in a ratio ofabout 1 weight part of chlorfenapyr to about 0.5-20 weight parts ofO,O,O′,O′-tetraethyl-S,S′-methylenebisphosphorodithioate.